EP2744447B1 - Thermoplastische mehrschichtige artikel - Google Patents

Thermoplastische mehrschichtige artikel Download PDF

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Publication number
EP2744447B1
EP2744447B1 EP12787072.3A EP12787072A EP2744447B1 EP 2744447 B1 EP2744447 B1 EP 2744447B1 EP 12787072 A EP12787072 A EP 12787072A EP 2744447 B1 EP2744447 B1 EP 2744447B1
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EP
European Patent Office
Prior art keywords
layer
multilayer article
thermoplastic
base layer
base
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Active
Application number
EP12787072.3A
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English (en)
French (fr)
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EP2744447A1 (de
Inventor
Goetz Thorwarth
Cyril Voisard
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DePuy Synthes Products Inc
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DePuy Synthes Products Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/80—Component parts, details or accessories; Auxiliary operations
    • B29C53/84—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00—Unspecified macromolecular compounds
    • B32B2398/20—Thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1043—Subsequent to assembly
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49826—Assembling or joining
    • Y10T29/49863—Assembling or joining with prestressing of part
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention generally relates to multilayer articles. More particularly, the present invention relates to multilayer articles suitable for implantation into a patient. Some embodiments of the invention relate to multilayer articles having one or more thermoplastic layers and one or more base layers. Further embodiments of the invention relate to methods for making multilayer articles.
  • US 2005/0021131 A1 discloses a stent made from one or more polmer layers, wherein the stent may change its shape at different temperatures depening on the glass transition temperatures of the polmer layers.
  • US 6,221,075 B1 discloses bone plates made of biocompatible, bioabsorbable thermoplastic material.
  • US 2002/0180101 A1 discloses an orthopedic implant formed from a sheet of moldable material.
  • US 2008/0154368 A1 discloses an orthopedic implant comprising a biocompatible sheath and a curable material sealed within the sheath
  • a multilayer article includes a thermoplastic layer having a first surface and a second surface opposite the first surface and a base layer have a first base surface and a second base surface opposite the first base surface, wherein the first base surface of the base layer is permanently bonded to the second surface of the thermoplastic layer, wherein the thermoplastic layer has a first glass transition temperature, T g I , and wherein the multilayer article is rigid at temperatures less than T g I and is flexible at temperatures greater than T g I .
  • the first base surface of the base layer is adjacent to the second surface of the thermoplastic layer.
  • the multilayer article includes a plurality of thermoplastic layers and plurality of base layers arranged in alternating layers.
  • the multilayer article includes an interlayer, for example, a diamond-like carbon layer, positioned between the thermoplastic layer and the base layer.
  • the thermoplastic layer is made from a material independently selected from the group consisting of: polyethylene terephthalate, polycaproamides, polytrimethylene carbonates, polyglycolide-co-trimethylene carbonates, poly(PBA-carbonates), poly(beta-hydroxybutyrate), polyhydroxybutyrate-hydroxyvaleric acids, and combinations thereof.
  • the thermoplastic layer is made from a material comprising a material selected from the group consisting of: polyethylene terephthalate, polycaproamides, polytrimethylene carbonates, polyglycolide-co-trimethylene carbonates, poly(PBA-carbonates), poly(beta-hydroxybutyrate), polyhydroxybutyrate-hydroxyvaleric acids, and combinations thereof.
  • the base layer is made from a biocompatible metallic material.
  • the biocompatible metallic material is independently selected from the group consisting of: titanium, titanium alloys, cobalt-chrome alloys, cobalt-chrome-molybdenum alloys, molybdenum alloys, tantalum, nitinol, GUMMETAL®, stainless steel and spring steel.
  • the base layer is made from a second thermoplastic material having a second glass transition temperature, T g II , which is at least 50 °C higher than T g I .
  • the second thermoplastic material is independently selected from the group consisting of: polycarbonate, polyaryl ether ketone, polyether ether ketone, polyether ketone ketone, fiber reinforced polyether ether ketone and fiber reinforced polyether ketone ketone, and combinations thereof.
  • an interface between the molten thermoplastic material and second thermoplastic material forms a contact angle of less than 5°.
  • a multilayer article of the present invention has a thickness ranging from 0.1 mm to 3.0 mm. In some embodiments, the multilayer article has a thickness ranging from 0.1 mm to 1.5 mm.
  • the present invention includes a bone plate made from a multilayer article. In other embodiments, the present invention includes, a thermally releasing spring element having a coil spring shape made from a multilayer article.
  • a method to form a multilayer article according to the present invention includes the steps of: (a) providing a base layer have a first base surface and a second base surface opposite the first base surface, the base layer having a thickness ranging from 0.5 mm to 0.01 mm; and (b) applying a thermoplastic layer to the first base surface of the base layer, the thermoplastic layer having a first glass transition temperature, T g I .
  • the method further includes repeating step (a) to form a multilayer article of at least ten alternating layers of the thermoplastic layer and the base layer.
  • the method includes applying heat and pressure to the layers.
  • the layers are heated to at least 200 °C for at least 1 minute to permanently affix the thermoplastic layers to the surface of the base layer.
  • the layers are heated to at least 10 °C higher than the melting temperature T m of the thermoplastic for at least 1 minute to permanently affix the thermoplastic layers to the surface of the base layer.
  • the multilayer article is rigid at temperatures less than T g I and is flexible at temperatures greater than T g I .
  • the base layer is made from a biocompatible metallic material.
  • the base layer includes a second thermoplastic material having a second glass transition temperature, T g II , which is at least 50 °C higher than T g I .
  • a method according to the present invention further includes coating the surface of the biocompatible metallic material with diamond like carbon to form a diamond like carbon interlayer positioned between the thermoplastic layer and the base layer. In further embodiments, the method also includes activating the diamond like carbon layer with oxygen plasma.
  • a method according to the present invention further includes cooling the multilayer article, and shaping the multilayer article to form a deformable implant. In other embodiments, the method includes rolling the multilayer article to form a coil spring shape.
  • a method for securing a plurality of bone fragments including: alternating layers of a thermoplastic layer and a base layer, the thermoplastic layer having a first surface and a second surface opposite the first surface and the base layer have a first base surface and a second base surface opposite the first base surface, wherein the first base surface of the base layer is adjacent to and permanently bonded to the second surface of the thermoplastic layer, wherein the thermoplastic layer has a first glass transition temperature, T g I ; and wherein the multilayer article is rigid at temperatures less than T g I and is flexible at temperatures greater than T g I .
  • the method further includes heating the laminate plate to a temperature greater than T g I to deform the laminate plate, wherein the laminate plate is deformable in at least one direction; and securing the deformed laminate plate to the plurality of bone fragments.
  • the method includes repeating the heating step a plurality of times.
  • the method further includes providing a thermally releasing spring element including a coiled multilayer article of alternating layers of a layer of thermoplastic material and a base layer, the thermoplastic layer having a first surface and a second surface opposite the first surface and the base layer have a first base surface and a second base surface opposite the first base surface, wherein the first base surface of the base layer is adjacent to and permanently bonded to the second surface of the thermoplastic layer, wherein the thermoplastic layer has a first glass transition temperature, T g I , and wherein the multilayer article is rigid at temperatures less than T g I and is flexible at temperatures greater than T g I .
  • a method includes heating the thermally releasing spring element to a temperature greater than T g I ; and inserting the thermally releasing spring element into holes within the deformed laminate plate to secure the deformed laminate plate to the plurality of bone fragments. In some embodiments, a method includes inserting the thermally releasing spring element into a cavity; and heating the thermally releasing spring element to a temperature greater than T g I , wherein heating the thermally releasing spring element causes the multilayer to at least partially uncoil in the cavity.
  • multilayer article 100 includes first thermoplastic layer 110 having first surface 112 and second surface 114 opposite first surface 112.
  • Multilayer article 100 further includes base layer 120 having first surface 122 and second surface 124 opposite first surface 122.
  • first surface 122 of base layer 120 is adjacent to and abuts second surface 114 of thermoplastic layer 110.
  • first surface 122 of base layer 120 is affixed to second surface 114 of thermoplastic layer 110.
  • first surface 122 is permenantly adhered to second surface 114, for example, by chemical bonds between first surface 122 and second surface 114.
  • First surface 122 and second surface 114 may be substantially isometric in at least one dimension. In some embodiments, first surface 122 and second surface 114 have substantially the same length. In some embodiments, first surface 122 and second surface 114 have substantially the same width. In some embodiments, first surface 122 and second surface 114 are substantially congruent. In some embodiments, first surface 122 and second surface 114 have substantially equal areas. While thermoplastic layer 110 and base layer 120 are shown in FIG. 1 as having substantially equal thicknesses, it should be understood that thermoplastic layer 110 and base layer 120 may have different thicknesses according to other embodiments of the invention. For example, thermoplastic layer 110 may have a thickness greater than the thickness of base layer 120 in one embodiment. In another embodiment, thermoplastic layer 110 may have a thickness less than the thickness of base layer 120. For purposes of this application, "substantially" means plus or minus 10% of the referenced dimension.
  • thermoplastic layer 110 may have a thickness ranging from: 1 mm to 0.01 mm; 1 mm to 0.1 mm; 1 mm to 0.5 mm; and 0.5 mm to 0.01 mm. In other embodiments, thermoplastic layer 110 may have a thickness of: less than 1 mm; less than 0.5 mm; or less than 0.1 mm. In some embodiments, the thermoplastic layer 110 may have a minimum thickness of about 0.01 mm. In some embodiment, base layer 120 may have thickness ranging from: 0.5 mm to 0.01 mm; 0.5 mm to 0.1 mm; 0.5 mm to 0.3 mm; and 0.3 mm to 0.01 mm.
  • base layer 120 may have thickness of: less than 0.5 mm; less than 0.3 mm; or less than 0.1 mm. In some embodiments, the base layer 120 may have a minimum thickness of about 0.01 mm. In certain embodiments, the thickness of thermoplastic layer 110 is chosen so it retains its shape during deformation and the thickness of base layer 120 is chosen so it is bendable.
  • FIG. 2 shows a multilayer article according to another exemplary embodiment of the invention.
  • multilayer article 200 includes first thermoplastic layer 210 having opposing first and second surfaces 212 and 214, and first base layer 220 having opposing first and second surfaces 222 and 224.
  • Thermoplastic layer 210 is affixed to base layer 220 by at least one interlayer 230 positioned between thermoplastic layer 210 and base layer 220.
  • interlayer 230 may be permanently bonded to both first surface 222 of base layer 220 and second surface 214 of thermoplastic layer 210.
  • interlayer 230 is chemically bonded to first surface 222 and/or surface 214.
  • interlayer 230 is covalently bonded to first surface 222 and/or surface 214.
  • first surface 122 and second surface 114, of the embodiment shown in FIG. 1 and first surface 222 of base layer 220 and second surface 214 of thermoplastic layer 210, of the embodiment shown in FIG. 2 , may be substantially congruent, have the same surface area, and/or be substantially isometric in at least one dimension.
  • first surface 222 and second surface 214 have substantially the same length and/or width.
  • the thickness of thermoplastic layer 210 may be the same as or different than the thickness of base layer 220.
  • interlayer 230 may have thickness that is less than the thickness of thermoplastic layer 210 or the thickness of base layer 220.
  • Thermoplastic layer 210 and base layer 220 may have any of the thicknesses as described above for thermplastic layer 110 and base layer 120.
  • a multilayer article according to other embodiments of the invention can have a plurality of thermoplastic layers and/or base layers.
  • the thermoplastic layers and base layers are configured in alternating arrangement.
  • a multilayer article includes a base layer positioned between and attached to two distinct thermoplastic layers.
  • a multilayer article includes a thermoplastic layer positioned between and attached to two separate base layers.
  • a multilayer article includes at least two thermoplastic layers.
  • a multilayer article includes multiple thermoplastic layers ranging from: 2 to 10 layers; 2 to 50 layers; 5 to 50 layers; 10 to 50 layers; 20 to 50 layers; 30 to 50 layers; and 40 to 50 layers.
  • a multilayer article includes: up to 10 double layer units; up to 20 double layer units; up to 30 double layer units; up to 40 double layer units; and up to 50 double layer units, wherein a double layer unit refers to a thermoplastic layer coupled to a base layer, for example, as shown in FIGS. 1 and 2 .
  • FIG. 3 shows an exemplary multilayer article having a plurality of thermoplastic layers and base layers in accordance with an embodiment of the present invention.
  • multilayer article 300 includes first thermoplastic layer 310 having opposing first and second surfaces 312 and 314, first base layer 320 having opposing first and second surfaces 322 and 324, second thermoplastic layer 330 having opposing first and second surfaces 332 and 334, and second base layer 340 having opposing first and second surfaces 342 and 344.
  • First base layer 320 is positioned between first and second thermoplastic layers 310 and 330
  • second thermoplastic layer 330 is positioned between first and second base layers 320 and 340.
  • first surface 322 of first base layer 320 is affixed to second surface 314 of first thermoplastic layer while second surface 324 of first base layer 320 is affixed to first surface 332 of second thermoplastic layer 330.
  • second surface 334 of second thermoplastic layer is affixed to first surface 342 of second base layer 340.
  • thermoplastic layers of the multilayer articles are composed of biocompatible polymer materials that become deformable when heated above their glass transition temperatures (Tg).
  • the biocompatible polymer materials are selected to be substantially rigid at temperatures below their Tg.
  • the material for the thermoplastic layers is selected to have a Tg in the range of about 35 °C to about 90 °C.
  • the material for the thermoplastic layers is selected to have a Tg in the range of about 35 °C to about 80 °C.
  • the material for the thermoplastic layers is selected to have a Tg in the range of about 35 °C to about 70 °C.
  • the material for the thermoplastic layers is selected to have a Tg above average human body temperature.
  • the material for the thermoplastic layers is selected to have a Tg above 37 °C.
  • the material for the thermoplastic layer is selected so that it is elastic at temperatures greater than its Tg. In some embodiments, the material for the thermoplastic layer is selected to have a melting point below the melting point of the base layer material. In some embodiments, the material for the thermoplastic layer is selected to have a melting point less than 300 °C. In some embodiments, the material for the thermoplastic layer is selected to have a melting point less than 200 °C. In some embodiments, the material for the thermoplastic layer is selected to have a melting point greater than Tg + 20 °C. In some embodiments, the material for the thermoplastic layer is selected to have a melting point greater than Tg + 30 °C. In some embodiments, the material for the thermoplastic layer is selected to have a melting point greater than Tg + 40 °C. In some embodiments, the material for the thermoplastic layer is selected to have a melting point greater than Tg + 50 °C.
  • the material for the thermoplastic layer is selected from non-resorbable polymers.
  • the thermoplastic layer may be made from a material independently selected from: polyethylene terephthalate, polycaproamides, poly(alpha-hydroxy esters), polycaprolactones, polytrimethylene carbonates, polyglycolide-co-trimethylene carbonates, poly(PBA-carbonates), poly(beta-hydroxybutyrate), polyhydroxybutyrate-hydroxyvaleric acids, and combinations thereof.
  • thermoplastic layer may be unsuitable for the thermoplastic layer according to certain embodiments including resorbable polymers that undergo biodegradation (through the action of water and/or enzymes to be chemically degraded) over a period of time.
  • resorbable polymers include polylactic acid and its variants, water soluble polymers such as polyvinyl alcohols.
  • thermoplastic layer examples include polylactides, poly(alpha-hydroxy esters), poly-L-lactide, poly-DL-lactide, poly-L-lactide-co-DL-lactide, polyglycolic acids, polyglycolide, polylactic-co-glycolic acids, polyglycolide-co-lactide, polyglycolide-co-DL-lactide, and polyglycolide-co-L-lactide.
  • thermoplastic layer in certain embodiments wherein a multilayer article includes more than one thermoplastic layer, for example as shown in FIG. 3 , two or more of the thermoplastic layers may be made of the same or different materials. In other embodiments, each of the thermoplastic layers in a multilayer article is made of the same material.
  • the base layers of the multilayer articles according to certain preferred embodiments of the present invention are composed of flexible and/or deformable sheets.
  • the base layers include flexible and/or deformable foils.
  • the material for the base layer is selected to exhibit flexural rigidity wherein Young's Modulus, E, is greater than 1 GPa.
  • the material for the base layer is selected to have a tensile strength greater than 20 MPa.
  • the material for the base layer is selected to have an elongation to failure value greater than 10 %.
  • the base layer is made from a biocompatible metallic material. In some embodiments, the base layer is made from a material substantially resistant to corrosion when implanted in a patient. In some embodiments, the base layer is in the form of a metallic foil. In some embodiments, the base layer may be made from titanium, titanium alloys, cobalt-chrome alloys, cobalt-chrome-molybdenum alloys, molybdenum alloys, tantalum, nitinol, GUMMETAL®, stainless steel, or spring steel such as tempered spring steel. Certain materials may be unsuitable for the base layer according to certain embodiments including biodegrading alloys such as Mg, Fe, Ca, alloys exhibiting stress-corrosion cracking or embrittlement or corroding metals such as Mg or Fe.
  • biodegrading alloys such as Mg, Fe, Ca, alloys exhibiting stress-corrosion cracking or embrittlement or corroding metals such as Mg or Fe.
  • the base layer is made from a high-strength biocompatible polymer material.
  • the high-strength biocompatible polymer material may have a tensile strength of at least 90 MPa.
  • the base layer is made from a polymer resistant to corrosion or degradation when implanted in a patient.
  • the material of the base layer has a glass transition temperature at least 50 °C higher than the Tg of the material selected for the thermoplastic layer.
  • the base layer may be made from a material selected from the group consisting of: polycarbonate, polyaryl ether ketone, polyether ether ketone, polyether ketone ketone, fiber reinforced polyether ether ketone and fiber reinforced polyether ketone ketone.
  • a multilayer article according to the present invention includes an interlayer between a thermoplastic layer and a base layer.
  • the interlayer aids in joining the thermoplastic layer and the base layer.
  • the interlayer contains different surface characteristics than the base layer, for example, having higher wettability and/or adhesion to the thermoplastic layer.
  • the interlayer demonstrates higher hydrophilicity than the base layer.
  • the interlayer may be subjected to surface activation to further enhance bonding with the thermoplastic layer.
  • the material of the thermoplastic layer demonstrates a contact angle of about 5° or less at the interface with the interlayer.
  • the interlayer includes a diamond-like carbon (DLC) coating which, for example, is applied to a surface of a base layer to which a thermoplastic layer is to be affixed.
  • DLC diamond-like carbon
  • the DLC coating can be subjected to surface activation.
  • the DLC coating is subjected to oxygen plasma treatment.
  • the interlayer includes materials with surface groups which may be activated by oxygen plasma.
  • materials include polymeric materials resulting from the deposition of organometallic alkoxide materials including titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide and titanium tetra-t-butoxide.
  • materials include amorphous silicon carbide layers resulting from deposition of tetramethylsilane, hexamethyldisilazane and hexamethyldisiloxane.
  • the interlayer includes chemical primers, for example, silanes.
  • Multilayer articles of certain preferred embodiments of the invention are designed to be substantially rigid at a first state and substantially deformable in a second state.
  • the multilayer articles according to some embodiments become deformable when heated to a temperature above the Tg of their thermoplastic layers.
  • the thermoplastic layers remain substantially rigid thereby preventing the base layer(s) affixed thereto from deforming.
  • the temperature of the thermoplastic layers is higher than Tg, the thermoplastic layers become deformable, which also permits deformation of the base layer(s) affixed thereto.
  • the transition from the substantially rigid state to the substantially deformable state of the multilayer articles is reversible, for example, such that the multilayer article becomes substantially rigid again once cooled to a temperature below Tg and retaining changes in shape imparted onto multilayer article in the deformable state.
  • substantially deformable means bendable by a force less than 200 N.
  • substantially rigid means not bendable by a force of at least 210 N.
  • the multilayer article of the present invention may be used to construct bone plates.
  • the bone plates may have any general shape known in the art suitable for bone fixation, osteosynthesis, compression and/or bone fusion.
  • Exemplary bone plates include one-dimensional bone plates.
  • the bone plates may have a generally linear or longitudinal configuration, for example as shown in U.S. Patent Application Publication No. US 2003/0004515 A1 .
  • Other exemplary bone plates that may be constructed from the multilayer articles of the present invention can be found in U.S. Patent Application Publication No. US 2008/0009872 A1 .
  • the bone plates constructed from the multilayer articles of the present invention are non-resorbable.
  • a bone plate constructed from a multilayer article according to certain embodiments of the present invention can be substantially rigid at body temperature (e.g., about 37 °C) but be deformed when heated to a temperature above Tg.
  • the bone plate may be heated to a temperature above Tg through exposure to a hot water bath, hot plate, irradiation, heat lamp, or other heat source known in the art. Accordingly, after heating to a temperature above Tg, the bone plate can be shaped or contoured to match a patient's specific anatomy. After cooling the bone plate to a temperature below Tg, the bone plate returns to a substantially rigid state while retaining the shape or contour to match the patient's anatomy.
  • FIGS. 4A and 4B show an example bone plate 400 in accordance with an embodiment of the present invention.
  • Bone plate 400 includes one or more biocompatible thermoplastic layers and one or more biocompatible base layers in accordance with embodiments described herein.
  • bone plate 400 defines one or more holes 460.
  • holes 460 are configured to receive a fastener therein, such as a bone screw, in order to secure bone plate 400 onto a surface. Holes 460 may or may not be countersunk. In the embodiment shown, holes 460 are substantially circular. In other embodiments, holes 460 may have any other shape or configuration known in the art.
  • bone plate 400 further defines one or more elongated slots 470 as shown. In some embodiments, holes 460 and/or elongated slots 470 extend through the entire thickness of bone plate 400 and may be formed by drilling through the layers.
  • bone plate 400 is substantially rigid at temperatures below the Tg value of the thermoplastic layers that it is constructed from. Upon heating bone plate 400 to a temperature above Tg, bone plate 400 may be deformed into any desired shape. Referring to FIG. 4B , for example, bone plate 400 may be contoured to conform to a patient's cranium 450 in one embodiment. In other embodiments, bone plate 400 may be deformed to fit upon other bones or anatomical structures of the patient.
  • a multilayer article according to the present invention can be configured as a thermally releasing spring element 500.
  • the thermally releasing spring element 500 includes at least a first thermoplastic layer 510 and at least a first base layer 520 made from an elastic material.
  • base layer 520 is made from spring steel such as tempered spring steel.
  • base layer 520 is made from Nitinol or GUMMETAL®.
  • Thermoplastic layer 510 may be made from any of the thermoplastic materials described herein. While spring element 500 is shown having a single base layer 520 and a single thermoplastic layer 510, it should be understood that spring element 500 may have a plurality of base layers and a plurality of thermoplastic layers as described above, for example, in alternating arrangement.
  • the thermally releasing spring element 500 When heated to a temperature above Tg for the thermoplastic layer 510, the thermally releasing spring element 500 becomes deformable and can be tensioned, for example, by coiling or rolling. When subsequently cooled to a temperature below Tg in the coiled or rolled configuration, the thermoplastic layer 510 because substantially rigid thereby retaining the coiled or rolled configuration of the thermally releasing spring element 500 with the elastic base layer 520 remaining under tension. If heated again to a temperature above Tg while unconstrained, the thermally releasing spring element 500 will uncoil as the elastic base layer 520 returns to its initial untensioned state.
  • the thermally releasing spring element 500 can include a central rod 550 around which the thermoplastic layer 510 and base layer 520 may be coiled. In some embodiments, spring element 500 expands radially from central rod 550 as it uncoils.
  • the thermally releasing spring element 500 can be used for fixation. Such thermally releasing spring elements may expand into existing or pre-drilled cavities. In such embodiments, the thermally releasing spring element 500 may lock an anchor in place without other mechanical devices. In some embodiments, the thermally releasing spring elements may take the form of an unthreaded screw. In other embodiments, the thermally releasing spring elements may take the form of a thread screw for improved pull-out resistance. In one such embodiment, a pin may have a thermally releasing spring wound around it which is fixed by the thermoplastic layer until released.
  • FIGS. 6A and 6B illustrate another embodiment of a thermally releasing spring used in an internal distractor 600 wherein a spring 620 is compressed and immobilized within a thermoplastic material 610 in a first configuration shown in FIG. 6A .
  • spring 620 is disposed between and fixed on both ends to implant components 630 and 640.
  • internal distractor 600 can have a first length L1.
  • spring 620 is made from an elastic material. In one embodiment, spring 620 is made from spring steel such as tempered spring steel. In other embodiments, spring 620 is made from nitinol or GUMMETAL®. In some embodiments, thermoplastic material 610 at least partially surrounds spring 620 and may be made from any of the thermoplastic materials described herein. In some embodiments, when thermoplastic material 610 is heated to a temperature at or above its Tg, spring 620 is allowed to expand (e.g., in an axial direction) to a second configuration shown in FIG. 6B . In some embodiments, internal distractor 600 in the second configuration has a second length L2, which is greater than first length L1.
  • internal distractor 600 can be used in a medical implant.
  • internal distractor 600 can be used to separate or maintain a gap between bones or bone fragments to which components 630 and 640 are affixed.
  • internal distractor 600 may be used in the mandible of a patient, for example, for the purposes described in U.S. Patent No. 6,666,869 .
  • components 630 and 640 may be bone plates or anchors affixed to bones separated previously by osteotomy.
  • distractor 600 can be used to slowly widen the gap between the separated bones by distraction as it expands, the gap being filled with new bone material for correction of deformities.
  • thermoplastic material 610 can be heated above Tg through the skin, for example, by infrared radiation or inductive heating.
  • inductive heating can be achieved by introducing a current into spring 620.
  • treating the surface of the base layer includes modifying the surface of the base layer to improve bonding with the thermoplastic layer. In some embodiments, treating the surface of the base layer includes modifying the surface of the base layer to improve wettability of the base layer. In some embodiments, treating the surface of the base layer includes modifying the surface of the base layer to increase hydrophilicity of the base layer. In some embodiments, treating the surface of the base layer includes cleaning the surface of the base layer, for example, using an organic solvent. In some embodiments, the surface of the base layer is treated to remove oxides, for example, via treatment with a base, sputtering by noble gas, and/or hydrogen ion beam exposure.
  • treating the surface of the base layer includes surface activation, for example, by plasma treatment.
  • plasma treatment creates reactive groups on the surface of the base layer which are capable of forming chemical bonds with the thermoplastic layer or an interlayer.
  • the base layer is made from a high-strength biocompatible polymer material as discussed previously herein.
  • the base layer is made from a biocompatible metallic material as discussed previously herein.
  • treating the surface of the base layer includes adding an interlayer that can also be subjected to subsequent surface activation.
  • treating the surface of the base layer includes providing an interlayer as discussed previously herein.
  • Such interlayers may be deposited onto the base layer via chemical vapor deposition, plasma assisted chemical vapor deposition or physical vapor deposition.
  • the interlayer material includes a DLC coating which is subjected to oxygen plasma treatment.
  • the plasma treatment leads to formation of reactive groups, such as -OH groups, on the hydrocarbon material, which can chemically connect to neighboring groups located on the thermoplastic layer.
  • the base layer is treated with vacuum oxygen plasma treatment.
  • Exemplary conditions include radio frequency plasma at a pressure of 1 ⁇ 10 -2 mbar oxygen and plasma power 20 Watts for area of 100 cm 2 .
  • the plasma treatment leads to formation of reactive groups (-OH) on the hydrocarbon material, which can chemically connect to neighboring groups, e.g., a molten thermoplastic.
  • surface activation is achieved through exposure of the base layer to UV radiation. Such activation may break bonds within the base layer material and subsequent desorption, leading to generation of a reactive surface.
  • the UV radiation used to treat the base layer is selected to have a wavelength of about 10 nm to about 260 nm.
  • the surface of the base layer may be activated by removing an oxide layer from the surface by treating with basic compounds, sputtering the layer with a noble gas or hydrogen ion beam.
  • a thermoplastic layer is superimposed onto the base layer, for example, after the surface of the base layer has been treated or activated.
  • a method for making a multilayer article includes preparing a stack of alternating base layers and thermoplastic layers.
  • the stack is formed by reactive injection molding of suitable monomers.
  • the thermoplastic layer is melted onto the base layer.
  • melting the thermoplastic layer onto the base layer includes heating the layers under pressure for example at temperatures of at least about 200 °C.
  • the layers are heated under pressure using a heated press.
  • the layers are heated under pressure using one or more heated rollers.
  • the layers are heated by microwave heating, induction heating, IR irradiation or DC current.
  • shaping the laminate includes cutting the laminate into a desired final shape.
  • the laminate is shaped using water jet cutting.
  • the laminate may be milled or drilled.
  • the laminate may be laser cut.
  • the laminate may be shaped by bending, deforming, molding, or rolling the laminate into a desired configuration.
  • shaping the laminate includes rolling the laminate to form a coil spring shape.
  • the laminate is shaped at a temperature at or above the glass transition temperature T g of the thermoplastic layer. In some embodiments, the laminate is shaped at a temperature between T g and the melting temperature T m of the thermoplastic layer.
  • An osteosynthesis plate which becomes deformable above the glass transition temperature of polyethylene terephthalate (PET) was fabricated by the following method:
  • a deformable cranial flap implant was produced by the following method:

Claims (13)

  1. Mehrschichtartikel (100; 200; 300), umfassend:
    eine thermoplastische Schicht (110; 210; 310, 330), die eine erste Oberfläche (112; 212; 312, 332) und eine zweite Oberfläche (114; 214; 314, 334) gegenüber der ersten Oberfläche (112; 212; 312, 332) aufweist; und
    eine Basisschicht (120; 220; 320, 340), die eine erste Basisoberfläche (122; 222; 322, 342) und eine zweite Basisoberfläche (124; 224; 324, 344) gegenüber der ersten Basisoberfläche (122; 222; 322, 342) aufweist;
    wobei die erste Basisoberfläche (122; 222; 322, 342) der Basisschicht (120; 220; 320, 340) mit der zweiten Oberfläche (114; 214; 314, 334) der thermoplastischen Schicht (110; 210; 310, 330) permanent verbunden ist, wobei die thermoplastische Schicht (110; 210; 310, 330) ein erstes thermoplastisches Material umfasst, das eine erste Glasübergangstemperatur, Tg I, aufweist; und wobei der Mehrschichtartikel (100; 200; 300) bei Temperaturen kleiner als Tg I fest ist und bei Temperaturen größer als Tg I flexibel ist,
    dadurch gekennzeichnet, dass die Basisschicht (120; 220; 320, 340) ein biokompatibles metallisches Material umfasst.
  2. Mehrschichtartikel nach Anspruch 1, des Weiteren umfassend eine Mehrzahl von thermoplastischen Schichten (310, 330) und eine Mehrzahl von Basisschichten (320, 340), die in abwechselnden Schichten angeordnet sind.
  3. Mehrschichtartikel nach einem der Ansprüche 1 und 2, wobei die thermoplastische Schicht (110; 210; 310, 330) ein Material umfasst, ausgewählt aus der Gruppe, bestehend aus: Polyethylenterephthalat, Polycaproamide, Polycaprolactone, Polytrimethylencarbonate, Polyglycolid-Co-Trimethylencarbonate, Poly(PBA-Carbonate), Poly(beta-Hydroxybutyrat), Polyhydroxybutyrat-Hydroxyvaleriansäuren und Kombinationen davon.
  4. Mehrschichtartikel nach einem der Ansprüche 1 bis 3, wobei das biokompatible metallische Material ein Material umfasst, ausgewählt aus der Gruppe, bestehend aus: Titan, Titanlegierungen, Cobalt-Chrom-Legierungen, Cobalt-Chrom-Molybdän-Legierungen, Molybdän-Legierungen, Tantal, Nitinol, GUMMETAL®, Edelstahl und Federstahl.
  5. Mehrschichtartikel nach einem der Ansprüche 1 bis 4, wobei die thermoplastische Schicht (210) und die Basisschicht (220) durch eine amorphe Kohlenstoff-Zwischenschicht (230), die zwischen der thermoplastischen Schicht (210) und der Basisschicht (220) positioniert ist, permanent verbunden sind.
  6. Mehrschichtartikel nach einem der Ansprüche 1 bis 5, der eine Dicke im Bereich von 0,1 mm bis 3,0 mm aufweist.
  7. Mehrschichtartikel nach einem der Ansprüche 1 bis 6, der eine Dicke im Bereich von 0,1 mm bis 1,5 mm aufweist.
  8. Knochenplatte (400), hergestellt aus dem Mehrschichtartikel (100; 200; 300) nach einem der Ansprüche 1 bis 7.
  9. Thermisch entspannendes Federelement (500; 620), das eine Spiralfederform aufweist, hergestellt aus dem Mehrschichtartikel (100; 200; 300) nach einem der Ansprüche 1 bis 7.
  10. Verfahren zum Bilden eines Mehrschichtartikels (100; 200; 300), umfassend die Schritte:
    Bereitstellen einer Basisschicht (120; 220; 320, 340), die eine erste Basisoberfläche (122; 222; 322, 342) und eine zweite Basisoberfläche gegenüber der ersten Basisoberfläche (122; 222; 322, 342) aufweist;
    Aufbringen einer thermoplastischen Schicht (110; 210; 310, 330) auf die erste Basisoberfläche (122; 222; 322, 342) der Basisschicht (120; 220; 320, 340), um einen Mehrschichtartikel (100; 200; 300) zu bilden, wobei die thermoplastische Schicht (110; 210; 310, 330) eine Schmelztemperatur, Tm, und eine erste Glasübergangstemperatur, Tg I, aufweist;
    Aufbringen von Druck auf den Mehrschichtartikel (100; 200; 300);
    Erwärmen des Mehrschichtartikels (100; 200; 300) auf zumindest 10 Grad C über Tm für zumindest 1 Minute, um die thermoplastische Schicht an der Oberfläche der Basisschicht (120; 220; 320, 340) permanent zu fixieren, und
    wobei der Mehrschichtartikel (100; 200; 300) bei Temperaturen kleiner als Tg I fest ist und bei Temperaturen größer als Tg I flexibel ist,
    dadurch gekennzeichnet, dass die Basisschicht (120; 220; 320, 340) ein biokompatibles metallisches Material umfasst.
  11. Verfahren nach Anspruch 10, des Weiteren umfassend die Schritte:
    Beschichten der Oberfläche (222) des biokompatiblen metallischen Materials mit amorphem Kohlenstoff, um eine amorphe Kohlenstoff-Zwischenschicht (230) zu bilden, die zwischen der thermoplastischen Schicht (210) und der Basisschicht (220) positioniert ist; und
    Aktivieren der amorphen Kohlenstoffschicht (230) mit Sauerstoffplasma.
  12. Verfahren nach Anspruch 10 oder 11, des Weiteren umfassend die Schritte:
    Abkühlen des Mehrschichtartikels (100; 200; 300) und
    Formen des Mehrschichtartikels (100; 200; 300), um ein verformbares Implantat (400) zu bilden.
  13. Verfahren nach Anspruch 10 oder 11, des Weiteren umfassend den Schritt:
    Aufrollen des Mehrschichtartikels (100; 200; 300), um eine Spiralfederform zu bilden.
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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11095994B2 (en) * 2013-02-15 2021-08-17 Cochlear Limited Conformable pad bone conduction device
WO2015095126A1 (en) * 2013-12-20 2015-06-25 Hartdegen Vernon Polyaxial locking hole
EP3086820B1 (de) * 2013-12-26 2020-10-28 Tepha, Inc. Medizinische implantate mit laminaten aus poly-4-hydroxybutyrat und copolymeren davon
US11202626B2 (en) 2014-07-10 2021-12-21 Crossroads Extremity Systems, Llc Bone implant with means for multi directional force and means of insertion
AU2015287901A1 (en) 2014-07-10 2017-02-23 Crossroads Extremity Systems, Llc Bone implant and means of insertion
EP3191006A1 (de) * 2014-09-12 2017-07-19 Brainlab AG Immobilisierungsmaske
US10130358B2 (en) 2015-10-07 2018-11-20 Arthrex, Inc. Devices for controlling the unloading of superelastic and shape memory orthopedic implants
TWI726940B (zh) * 2015-11-20 2021-05-11 美商泰坦脊柱股份有限公司 積層製造整形外科植入物之方法
EP3393537A1 (de) 2015-12-22 2018-10-31 Access Vascular, Inc. Hochfeste biomedizinische materialien
TWI577324B (zh) * 2015-12-30 2017-04-11 Applicable to hot melt implantation to bone correction or bone defect
US11864753B2 (en) 2017-02-06 2024-01-09 Crossroads Extremity Systems, Llc Implant inserter
WO2018148284A1 (en) 2017-02-07 2018-08-16 Crossroads Extremity Systems, Llc Counter-torque implant
CN106983551B (zh) * 2017-05-12 2019-06-14 国家康复辅具研究中心 刚度梯度变化的多孔复合骨板及其制备方法
CA3067850A1 (en) * 2017-06-21 2018-12-27 Access Vascular, Inc High strength porous materials incorporating water soluble polymers
USD961081S1 (en) 2020-11-18 2022-08-16 Crossroads Extremity Systems, Llc Orthopedic implant
TWI830066B (zh) * 2021-09-29 2024-01-21 南臺學校財團法人南臺科技大學 醫療植入物及其製造方法

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3721597A (en) * 1969-05-02 1973-03-20 Dow Chemical Co Bonding metal laminae with thermoplastic film
DE3601715A1 (de) * 1986-01-22 1987-07-23 Heinl Thomas Chirurgisches instrumentenset zum verbinden von knochenfragmenten
FI82805C (fi) * 1988-12-23 1991-04-25 Biocon Oy En polymer fixeringskivkonstruktion foer kirurgiskt bruk.
US5779706A (en) * 1992-06-15 1998-07-14 Medicon Eg Surgical system
US5576072A (en) * 1995-02-01 1996-11-19 Schneider (Usa), Inc. Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with at least one other, dissimilar polymer hydrogel
JPH08257132A (ja) * 1995-03-20 1996-10-08 Piolax Inc 医療用ガイドワイヤ
US6626939B1 (en) * 1997-12-18 2003-09-30 Boston Scientific Scimed, Inc. Stent-graft with bioabsorbable structural support
US6221075B1 (en) * 1998-03-06 2001-04-24 Bionx Implants Oy Bioabsorbable, deformable fixation plate
US6533454B1 (en) * 1999-09-30 2003-03-18 Bionx Implants Oy Surgical system for tissue fixation
DE69919911T2 (de) 1999-12-06 2005-09-15 Synthes Ag Chur, Chur Resorbierbare knochenplatte
CA2401439C (en) 2000-02-29 2007-11-27 Synthes (U.S.A.) Endo-distractor
US6613089B1 (en) * 2000-10-25 2003-09-02 Sdgi Holdings, Inc. Laterally expanding intervertebral fusion device
US7297394B2 (en) * 2002-03-01 2007-11-20 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials
US6736848B2 (en) * 2001-05-29 2004-05-18 Sdgi Holdings, Inc. Method and apparatus for using formable polymers for orthopedic support
TWI304321B (en) * 2002-12-27 2008-12-11 Toray Industries Layered products, electromagnetic wave shielding molded articles and method for production thereof
US7927703B2 (en) * 2003-04-11 2011-04-19 3M Innovative Properties Company Adhesive blends, articles, and methods
US8298292B2 (en) * 2003-04-16 2012-10-30 Howmedica Osteonics Corp. Craniofacial implant
JP2007516314A (ja) * 2003-05-22 2007-06-21 ザイベックス コーポレーション ナノコンポジットおよびナノコンポジットに関する方法
US7172814B2 (en) * 2003-06-03 2007-02-06 Bio-Tec Biologische Naturverpackungen Gmbh & Co Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends
AU2004246998A1 (en) * 2003-06-16 2004-12-23 Nanyang Technological University Polymeric stent and method of manufacture
US7931695B2 (en) * 2003-07-15 2011-04-26 Kensey Nash Corporation Compliant osteosynthesis fixation plate
US20050149032A1 (en) 2003-12-30 2005-07-07 Douglas Vaughen Resorbable surgical fixation device
US7195813B2 (en) * 2004-05-21 2007-03-27 Eastman Kodak Company Mixed absorber layer for displays
US20060062983A1 (en) * 2004-09-17 2006-03-23 Irvin Glen C Jr Coatable conductive polyethylenedioxythiophene with carbon nanotubes
WO2006108114A2 (en) * 2005-04-01 2006-10-12 The Regents Of The University Of Colorado A graft fixation device and method
US20060247638A1 (en) * 2005-04-29 2006-11-02 Sdgi Holdings, Inc. Composite spinal fixation systems
US7967820B2 (en) * 2006-02-07 2011-06-28 P Tech, Llc. Methods and devices for trauma welding
US20070207284A1 (en) * 2006-03-02 2007-09-06 Mcclintic Shawn A Barrier article and method
NL2000100C2 (nl) * 2006-06-13 2007-12-14 Gtm Consulting B V Laminaat uit metaalplaten en kunststof.
WO2008005936A2 (en) * 2006-06-30 2008-01-10 Buckeye Technologies Inc. Fire retardant nonwoven material and process for manufacture
US7771476B2 (en) * 2006-12-21 2010-08-10 Warsaw Orthopedic Inc. Curable orthopedic implant devices configured to harden after placement in vivo by application of a cure-initiating energy before insertion
US20080171306A1 (en) * 2007-01-17 2008-07-17 Goldberg Artie J Translucent, isotropic endodontic post
US20080234753A1 (en) * 2007-03-19 2008-09-25 Warsaw Orthopedic, Inc. Spinal Stabilization Systems
US20080274360A1 (en) * 2007-05-04 2008-11-06 General Electric Company Polyaryl ether ketone - polycarbonate copolymer blends
US8292925B2 (en) * 2007-06-19 2012-10-23 Zimmer Spine, Inc. Flexible member with variable flexibility for providing dynamic stability to a spine
DE102007034169A1 (de) * 2007-07-23 2009-01-29 Karl Leibinger Medizintechnik Gmbh & Co. Kg Medizinisches Synthesesystem und Verfahren zur Verbindung eines mehrteiligen medizinischen Synthesesystems
JP5567023B2 (ja) * 2008-10-23 2014-08-06 ダブリュ・ダブリュ・テクノロジー・アクチェンゲゼルシャフト 対象物を硬組織に固定するための増強装置
EP2459372A4 (de) * 2009-07-27 2012-12-19 Univ North Carolina State Auf wärme reagierende verbundmaterialien
JP6385675B2 (ja) * 2010-09-30 2018-09-05 スパインウェルディング・アクチェンゲゼルシャフトＳｐｉｎｅｗｅｌｄｉｎｇ Ａｇ 外科用安定化プレート、外科用安定化プレートを埋め込む方法およびシステム
WO2013010282A1 (en) * 2011-07-18 2013-01-24 Woodwelding Ag Method and implant for stabilizing separated bone portions relative to each other
US8414654B1 (en) * 2011-11-23 2013-04-09 Amendia, Inc. Bone implants and method of manufacture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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JP6096190B2 (ja) 2017-03-15
WO2013024355A1 (en) 2013-02-21
EP2744447A1 (de) 2014-06-25
TW201320985A (zh) 2013-06-01
US20130046346A1 (en) 2013-02-21
JP2014529518A (ja) 2014-11-13

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